Halogenated vat dyestuffs and process of making same



November 1, 1926.

Patented May 5, 1931 UNITED STATES PATENT OFFICE RICHARD HERZ, OF FRANKFORT-ON-THE-MAIN, AND \VERNER ZERWECK, OF FRANK- FORT-ON-THE-MAIN-FECHIENHEIM, GERMANY, ASSIGNOBS TO GENERAL ANILINE WORKS, INC., OIEXNEW YORK, N. Y., A CORPORATION OF DELAWARE vHALOGrlilNA'DED VAT DYESTUFES AND PROCESS OF MAKING SAME No Drawing. Original application filed November 1, 1926, Serial No. 145,697, and in Germany November 7,

' 1925. Divided and this application filed December 11, 1829. Serial No. 413,420,

This application is a division of our copending application Serial No.- 145,697, filed lVe have found that valuable vat dyestuffs of the anthanthrone series are obtainable by causing a halogenating agent to act upon anthanthrone in the presence of an inorganic diluent selected from the group consisting of: concentrated sulfuric acid, sulfuric acid monohydrate, fuming sulfuric acid, chlorosulfonic acid, sulfuryl chloride, sulfur chlorides and thionyl chloride. The reaction can be carried out at ordinary or at elevated temperatures preferably below 1009 c.

As suitable halogenating agents there may be used: bromine, chlorine gas, and for chlorinating also those compounds which evolve chlorine duringthe reaction as, for instance, sulfuryl chloride, antimony pentachloride, sulfur chlorides, alkali hypochlorites in the presence of an inorganic acid,

' and alkali chlorates in the presence of hydrochloric acid.

According to our new process, chlorine and bromine atoms may be introduced in the anthanthrone molecule by treating finely ground anthanthrone with bromine in the presence of an inorganic diluent asbefore stated, and then passing chlorine into this mixture, to which a small amount of iodine, ferric chloride, antimony pentachloride, iodine-trichloride or a similar compound may be added as a halogen carrier.

The most valuable products are obtained when the chlorination and bromination are carried out in such a way that approximately one atom of chlorine and one atom of bromine enter into the molecule of the anthanthrone.

The new dyestufl', corresponding probably to the general formula: I

in which formula X is approximately the number 1, is when dry an orange powder, diilicultly soluble in organic solvents of a higher boiling point, easily soluble in concentrated sulfuric acid with a pure green color, and dyeing vegetable fibers from a violet vat orange shades of exceptional brightness and excellent fastness.

In order to further illustrate our invention, the following example is given, the parts being by weight and all temperatures in centigrade degrees, but it is understood that our invention is not limited to the par ticular products or reaction condition mentioned therein:

Ewample 22 parts of anthanthrone are dissolved in about 200 parts of sulfuric acid monohydrate, 42 parts of fuming sulfuric acid of taine'd, having probably the formula:

in which formula X is approximately the number 1, is when dry an orange powder, diilicultly soluble in organic solvents of a higher boiling point, easily soluble in concentrated sulfuric acid with a pure green color, and dyeing vegetable fibers from a violetvat orangeshades of exceptional brightness and excellent fastness.

\Ve claim:

1. The process which comprises reacting upon anthanthrone with a brominating agent, in the presence of an inorganic diluent selected from the group consisting of concentrated sulfuric acid, sulfuric acid monohydrate, fuming sulfuric acid, chlorosulfonic acid, sulfuryl chloride, sulfur chlorides and thionyl chloride, at an elevated temperature below 100 C., and then cooling down and passing chlorine into the mixture.

2. The process WAlCll comprises reacting upon anthanthrone with a brominating agent, in the presence of an inorganic diluent selected from the group consisting of concentrated sulfuric acid, sulfuric acid monohydrate, fuming sulfuric acid, chlorosulfonic acid, sulfuryl chloride, sulfur chlorides and thionyl chloride, and of a carrier selected from the group consisting of I, SbCh, FeCl and 161 at an elevated temperature below 100 (1., and then cooling down and passing chlorine into the mixture.

3. T he process which comprises reacting upon anthanthrone with a brominating agent, in the presence of an inorganic diluent selected from the group consisting of concentrated sulfuric acid, sulfuric acid monohydrate, fuming sulfuric acid, chlorosulfonic acid, sulfuryl chloride, sulfur chlorides and thionyl chloride, at an elevated temperature below 100 (3., until approximately one bromine atom has been introduced into the anthanthrone molecule, and then cooling down and passing chlorine into the mixture, until approximately one chlorine atom has been introduced into the anthanthrone molecule.

4:. The process which comprises reacting upon anthanthrone with a brominating agent, in the presence of an inorganic diluent selected from the group consisting of concentrated sulfuric acid, sulfuric acid monohydrate, fuming sulfuric acid, chlorosulfonic acid, sulfuryl chloride, sulfur chlorides and thionyl chloride, and of a carrier selected from the group consisting of l, SbCh, FeLl and 101 at an elevated temperature below 100 6., until approximately one bromine atom has been introduced into the anthanthrone molecule, and then cooling down and passing chlorine into the mixture, until approximately one chlorine atom has been introduced into the anthanthrone molecule.

5. The process which comprises reacting upon anthanthrone with bromine in the pres ence of sulfuric acid monohydrate and a small amount of iodine, at a temperature of about 60", until approximately one bromine atom has been introduced into the anthanthrone molecule, and then cooling down and passing chlorine into the mixture, until approximately one chlorine atom has been introduced into the anthanthrone molecule.

soas 6. new products, vat dyestuffs corresponding probably to the formula J CIA-Br, O

in which formula x is approximately the number 1, are when dry orange powders, diiiicultly soluble in organic solvents of a higher boiling point, easily soluble in concentrated sulfuric acid with a pure green color, and dyeing vegetable fibers from a violet vat orange shades of exceptional brightness and excellent fastness.

In testimony whereof we afiix our signatures.

RICHARD HERZ.

l VERNER ZERVVECK. 

